Indolin derivaties as sun protection agents

ABSTRACT

There is described the use of indoline derivatives of formula  
                 
 
     wherein  
     R 1  is hydrogen; C 1 -C 5 alkyl; C 1 -C 18 alkoxy; or halogen;  
     R 2  is C 1 -C 8 alkyl; C 5 -C 7 cycloalkyl; C 6 -C 10 aryl;  
     R 3  is C 1 -C 18 alkyl or a radical of formula (1a)  
                 
 
     R4 is hydrogen; or a radical of formula  
                 
 
     R 5  is  
                 
 
     C 1 -C 18 alkoxy; or a radical of formula  
                 
 
     R 6  and R 7  are each independently of the other hydrogen; or C 1 -C 5 alkyl;  
     R 8  is hydrogen; C 1 -C 5 alkyl; C 5 -C 7 cycloalkyl; phenyl; phenyl-C 1 -C 3 alkyl;  
     R 9  is C 1 -C 18 alkyl;  
     X is halogen; a radical of formula (1c)  
                 
 
                 
 
     and  
     n is 0; or 1,  
     as light-protective agents.

[0001] The present invention relates to indoline derivatives and to theuse of those compounds as light-protective agents.

[0002] Indoline compounds are known from dye chemistry, where they areused as intermediates or starting materials. Indoxyl, for example,occurs as an intermediate in industrial indigo synthesis.Trimethyl-2-methyleneindoline (Fischer base) is used as startingcompound in the preparation of polymethine dyes.

[0003] It has been found, surprisingly, that certain indolinederivatives are also suitable as light-protective agents.

[0004] The present invention accordingly relates to the use of indolinederivatives of formula

[0005] wherein

[0006] R₁ is hydrogen; C₁-C₅alkyl; C₁-C₁₈alkoxy; or halogen;

[0007] R₂ is C₁-C₈alkyl; C₅-C₇cycloalkyl; C₆-C₁₀aryl;

[0008] R₃ is C₁-C₁₈alkyl; or a radical of formula (1a)

[0009] R₄ is hydrogen; or a radical of formula (1b)

[0010] R₅ is a radical of formula (1c)

[0011] C₁-C₁₈alkoxy; or a radical of formula

[0012] R₆ and R₇ are each independently of the other hydrogen; orC₁-C₅alkyl;

[0013] R₈ is hydrogen; C₁-C₉alkyl; C₅-C₇cycloalkyl; phenyl;phenyl-C₁-C₃alkyl;

[0014] R₉ is C₁-C₁₈alkyl;

[0015] X is halogen; a radical of formula (1e)

[0016] or

[0017] and

[0018] n is 0; or 1,

[0019] as light-protective agents.

[0020] C₁-C₁₈Alkyl denotes straight-chain or branched alkyl radicals,for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, amyl, isoamyl or tert-amyl, hexyl, heptyl, octyl, isooctyl,nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl or octadecyl.

[0021] C₁-C₁₈Alkoxy is, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy ortert-amyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy,decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy,hexadecyloxy, heptadecyloxy or octadecyloxy.

[0022] Halogen is fluorine or bromine, and especially chlorine.

[0023] C₅-C₇Cycloalkyl is, for example, cyclopentyl, cycloheptyl andespecially cyclohexyl.

[0024] C₆-C₁₀Aryl is phenyl or naphthyl.

[0025] Preference is given according to the invention to the use ofcompounds of formula (1) wherein

[0026] R₅ is a radical of formula (1g)

[0027] and

[0028] R₈ is hydrogen; C₁-C₅alkyl; or phenyl, especially hydrogen ormethyl.

[0029] Also of interest are compounds of formula (1) wherein

[0030] R₅ is C₁-C₁₈alkoxy, and especially a radical of formula

[0031] Also of interest are compounds of formula (1) wherein

[0032] R₅ is a radical of formula

[0033] and

[0034] R₈ is hydrogen; or methyl.

[0035] Of special interest are also compounds of formula (1) wherein R₃is C₃-C₁₈isoalkyl.

[0036] Exemplary compounds used in accordance with the inventioncorrespond to formulae

[0037] Some of the compounds of formulae (1) to (11) are known compoundswhile some are new compounds.

[0038] The new compounds correspond to formula

[0039] wherein

[0040] R₁ is hydrogen; C₁-C₅alkyl; C₁-C₅alkoxy; or halogen;

[0041] R₂ is C₁-C₅alkyl; C₅-C₇cycloalkyl; C₆-C₁₀aryl;

[0042] R₃ is C₁-C₅alkyl or a radical of formula (1a)

[0043] R₄ is hydrogen; or a radical of formula (1b)

[0044] R₅ is C₅-C₁₈alkoxy; a radical of formula (1b); or a radical offormula

[0045] R₉ is C₁-C₁₈alkyl; or

[0046] R₄ and R₅ denote a radical of formula (1b).

[0047] The indoline derivatives used in accordance with the inventionare prepared in a manner known per se by means of condensation of theindoline compound (Fischer base) of formula

[0048] with the appropriate acid chloride or a CH acid compound to formthe compound of formula (1).

[0049] The reaction is usually carried out at temperatures of from 20 to110° C. in the presence of an inert solvent, for example petroleumether, toluene, xylene, a mixture of xylene isomers, or of a halogenatedhydrocarbon, for example CH₂Cl₂. The reaction can, however, also beperformed without solvents. The reaction time is usually a few minutesand may last for up to a few hours.

[0050] The compounds of formula (1) are especially suitable as UVfilters, that is to say for protecting ultraviolet-sensitive organicmaterials, especially the skin and hair of humans and animals, againstthe damaging action of UV radiation. The compounds are accordinglysuitable as light-protective agents in cosmetic, pharmaceutical andveterinary-medicinal compositions. The compounds can be used both indissolved form and in the micronised state.

[0051] The invention relates also to a cosmetic composition comprising acompound of formula (1).

[0052] For cosmetic use, these light-protective agents, unless they arewater-soluble, usually have an average particle size in the range from0.02 to 2, preferably from 0.05 to 1.5, and very especially from 0.1 to1.0, m. The insoluble light-protective agents in accordance with theinvention can be brought to the desired particle size by customarymethods, e.g. grinding with, for example, a jet, ball, vibration orhammer mill. Preference is given to performing the grinding in thepresence of from 0.1 to 30% by weight, preferably from 0.5 to 15% byweight, based on the UV absorber, of a grinding aid, for example analkylated vinylpyrrolidone polymer, a vinylpyrrolidone-vinyl acetatecopolymer, an acyl glutamate, an alkyl polyglucoside or, especially, aphospholipid.

[0053] The light-protective agents can also be used dry in powder form.For that purpose, the light-protective agents are subjected to knowngrinding processes such as vacuum atomisation, countercurrentspray-drying etc. Such powders have a particle size of from 0.1 nm to 2μm. To avoid agglomeration processes, the light-protective agents can becoated, before the pulverisation process, with a surface-activecompound, for example an anionic, non-ionic or amphoteric surfactant,for example with phospholipids or known polymers, such as PVP, acrylatesetc.

[0054] The cosmetic composition, in addition to comprising the UVabsorber according to the invention, may also comprise one or morefurther UV-protective substances of the following classes of substance:

[0055] 1. p-aminobenzoic acid derivatives, e.g. 4-dimethylaminobenzoicacid 2-ethylhexyl ester;

[0056] 2. salicylic acid derivatives, e.g. salicylic acid 2-ethylhexylester;

[0057] 3. benzophenone derivatives, e.g. 2-hydroxy-4-methoxybenzophenoneand the 5-sulfonic acid derivative thereof;

[0058] 4. dibenzoylmethane derivatives,e.g.1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione;

[0059] 5. diphenyl acrylates, e.g. 2-ethylhexyl-2-cyano-3,3-diphenylacrylate and 3-(benzo-furanyl)-2-cyanoacrylate;

[0060] 6. 3-imidazol-4-yl-acrylic acid and esters;

[0061] 7. benzofuran derivatives, especially 2-(p-aminophenyl)benzofuranderivatives, described in EP-A-582 189, U.S. Pat. No. 5,338,539, U.S.Pat. No. 5,518,713 and EP-A-613 893;

[0062] 8. polymeric UV absorbers, e.g. the benzylidene malonatederivatives described in EP-A-709 080;

[0063] 9. cinnamic acid derivatives, e.g. the 4-methoxycinnamic acid2-ethylhexyl ester and isoamyl ester or cinnamic acid derivativesdisclosed in U.S. Pat. No. 5,601,811 and WO 97/00851;

[0064] 10. camphor derivatives, e.g.3-(4′-methyl)benzylidene-bornan-2-one, 3-benzylidene-bornan-2-one,N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer,3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate,3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic acid) and salts,3-(4′-sulfo)benzylidene-bornan-2-one and salts;

[0065] 11. trianilino-s-triazine derivatives, e.g.2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and the UVabsorbers disclosed in U.S. pat. No. 5,332,568, EP-A-517 104, EP-A-507691, WO 93/17002 and EP-A-570 838;

[0066] 12. 2-hydroxyphenylbenzotriazole derivatives;

[0067] 13. 2-phenylbenzimidazole-5-sulfonic acid and salts thereof;

[0068] 14. menthyl-o-aminobenzoate;

[0069] 15. inorganic micropigments, for example TiO₂ (variouslyencapsulated);

[0070] 16. N-substituted benzimidazoles, as described in EP-A-0 843 995;

[0071] 17. hydroxyphenylbenzotriazoles and derivatives, especiallysiloxane derivatives;

[0072] 18. siloxanes of oxanilide derivatives, as described in EP-A-0712 856.

[0073] The UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N.A. Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics &Toiletries (107), 50ff (1992) can also be used as additionalUV-protective substances in the formulation according to the invention.

[0074] Furthermore, the cosmetic composition according to the inventioncan also be used together with known antioxidants, for example aminoacids (e.g. glycerol, histidine, tyrosine, tryptophan) and derivativesthereof, peptides (e.g. carnosine) and derivatives thereof, vitamin Eand vitamin A and derivatives thereof, derivatives of vitamin C,carotenoids, flavanoids and derivatives thereof and ubiquinones or HALS(=“Hindered Amine Light Stabilizers”) compounds.

[0075] The cosmetic compositions contain from 0.1 to 15% by weight,preferably from 0.5 to 10% by weight, based on the total weight of thecomposition, of a light-protective agent of formula (1) or of a mixtureof light-protective agents, and a cosmetically tolerable adjuvant.

[0076] The cosmetic compositions can be prepared by physically mixingthe UV absorber(s) with the adjuvant using customary methods, forexample by simply stirring the individual components together,especially by utilising the dissolution characteristics of knowncosmetic UV absorbers, for example OMC, salicylic acid isooctyl ester,among others.

[0077] The cosmetic compositions may be formulated as a water-in-oil oroil-in-water emulsion, as an oil-in-alcohol lotion, as a vesiculardispersion of an ionic or non-ionic amphiphilic lipid, as a gel, a solidstick or as an aerosol formulation.

[0078] In the case of a water-in-oil or oil-in-water emulsion, thecosmetically tolerable adjuvant contains preferably from 5 to 50% of anoily phase, from 5 to 20% of an emulsifier and from 30 to 90% water. Theoily phase may contain any oil suitable for cosmetic formulations, e.g.one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, afatty acid ester or a fatty alcohol. Preferred mono- or poly-ols areethanol, isopropanol, propylene glycol, hexylene glycol, glycerol andsorbitol. Di- or/and tri-valent metal salts (alkaline earth metal, Al³⁺,among others) of one or more alkylcarboxylic acids may also be used.

[0079] For the cosmetic compositions it is possible to use anyconventionally used emulsifier, for example one or more ethoxylatedesters of natural derivatives, e.g. polyethoxylated esters ofhydrogenated castor oil; or silicone oil emulsifiers, e.g. siliconepolyol; fatty acid soaps, which may or may not be ethoxylated; fattyalcohols or fatty acids and polyoxyethylene derivatives thereof;sorbitan esters, which may or may not be ethoxylated; ethoxylated fattyacids or fatty acid esters; or ethoxylated glycerides.

[0080] Further suitable emulsifiers are fatty acid partial esters ofpolyhydric alcohols such as glycol, 1,2-propylene glycol, glycerol,sorbitol and pentaerythritol, and also protein-fatty acid condensationproducts and lanolin derivatives, salts of alkylcarboxylic acids, ofalkyl sulfates or sulfonates or of polyglycol ethers. Mixtures ofanionic and non-ionic emulsifiers or mixtures of purely non-ionicsurface-active substances having different HLB values may also be used.Mixtures of fatty alcohol and fatty acid polyglycol ethers or ofoxethylated fats are also customary.

[0081] The cosmetic compositions may also comprise further components,e.g. emollients, emulsion stabilisers, skin hurmectants, skin-tanningaccelerators, thickeners, e.g. xanthan, moisture-retaining agents, e.g.glycerol, preservatives, perfumes and colourings.

[0082] Cosmetic formulations according to the invention are contained ina variety of cosmetic preparations. Especially the followingpreparations, for example, come into consideration:

[0083] skin-care preparations, e.g. skin-washing and cleansingpreparations in the form of tablet-form or liquid soaps, soaplessdetergents or washing pastes;

[0084] bath preparations, e.g. liquid (foam baths, milks, showerpreparations) or solid bath preparations, e.g. bath cubes and bathsalts;

[0085] skin-care preparations, e.g. skin emulsions, multi-emulsions orskin oils;

[0086] cosmetic personal care preparations, e.g. facial make-up in theform of day creams or powder creams, face powder (loose and pressed),rouge or cream make-up, eye-care preparations, e.g. eyeshadowpreparations, mascara, eyeliner, eye creams or eye-fix creams; lip-carepreparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-carepreparations, such as nail varnish, nail varnish removers, nailhardeners or cuticle removers;

[0087] intimate hygiene preparations, e.g. intimate washing lotions orintimate sprays;

[0088] foot-care preparations, e.g. foot baths, foot powders, footcreams or foot balsams, special deodorants and antiperspirants orcallus-removing preparations;

[0089] light-protective preparations, such as sun milks, lotions, creamsand oils, sun blocks or tropicals, pre-tanning preparations or after-sunpreparations;

[0090] skin-tanning preparations, e.g. self-tanning creams;

[0091] depigmenting preparations, e.g. preparations for bleaching theskin or skin-lightening preparations;

[0092] insect-repellents, e.g. insect-repellent oils, lotions, sprays orsticks;

[0093] deodorants, such as deodorant sprays, pump-action sprays,deodorant gels, sticks or roll-ons;

[0094] antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;

[0095] preparations for cleansing and caring for blemished skin, e.g.soapless detergents (solid or liquid), peeling or scrub preparations orpeeling masks;

[0096] hair-removal preparations in chemical form (depilation), e.g.hair-removing powders, liquid hair-removing preparations, cream- orpaste-form hair-removing preparations, hair-removing preparations in gelform or aerosol foams;

[0097] shaving preparations, e.g. shaving soap, foaming shaving creams,non-foaming shaving creams, foams and gels, preshave preparations fordry shaving, aftershaves or after-shave lotions;

[0098] fragrance preparations, e.g. fragrances (eau de Cologne, eau detoilette, eau de parfum, parfum de toilette, perfume), perfume oils orcream perfumes;

[0099] dental-care, denture-care and mouth-care preparations, e.g.toothpastes, gel toothpastes, tooth powders, mouthwash concentrates,anti-plaque mouthwashes, denture cleaners or denture fixatives;

[0100] cosmetic hair-treatment preparations, e.g. hair-washingpreparations in the form of shampoos and conditioners, hair-carepreparations, e.g. pretreatment preparations, hair tonics, stylingcreams, styling gels, pomades, hair rinses, treatment packs, intensivehair treatments, hair-structuring preparations, e.g. hair-wavingpreparations for permanent waves (hot wave, mild wave, cold wave),hair-straightening preparations, liquid hair-setting preparations,foams, hairsprays, bleaching preparations, e.g. hydrogen peroxidesolutions, lightening shampoos, bleaching creams, bleaching powders,bleaching pastes or oils, temporary, semi-permanent or permanent haircolourants, preparations containing self-oxidising dyes, or natural haircolourants, such as henna or camomile.

[0101] The formulations mentioned may be presented in various forms, forexample

[0102] in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W orPIT emulsion or any kind of microemulsion,

[0103] in the form of a gel,

[0104] in the form of an oil, cream, milk or lotion,

[0105] in the form of a powder, lacquer, tablet or make-up,

[0106] in the form of a stick,

[0107] in the form of a spray (propellant-gas spray or pump-actionspray) or of an aerosol,

[0108] in the form of a foam, or

[0109] in the form of a paste.

[0110] The cosmetic formulations are distinguished by excellentprotection of human skin against the damaging effect of sunlight.

[0111] In the following Examples percentages refer to weight. Amountsrefer to the pure substance.

PREPARATION EXAMPLES EXAMPLE 1

[0112] 10 g of 2-(1,3,3-trimethyl-indolin-2-ylene) acetaldehyde(=Fischer base aldehyde; technical grade) are dissolved in 250 ml ofpetroleum ether (boiling range 80-110° C.) under reflux. The solution isclarified by means of filtration using 1 g of filtration aid and, withstirring, slowly cooled; after 16 hours, it is filtered at 25° C. anddried. 6 g of pure, slightly yellow crystals of formula

[0113] having a melting point of 105-106° C. are obtained.

[0114] ε=34520 l/(mol/cm) in ethanol at λ_(max)=341 nm:

[0115] photostability t_(½)=208 hours

Example 2

[0116] 5 g of 2-(1,3,3-trimethyl-indolin-2-ylene) acetaldehyde (=Fischerbase aldehyde) are dissolved in 50 ml of toluene. There are then added 5drops of piperidine and 0.5 g of 100% acetic acid; 5 g of cyanoaceticacid 2-ethyl ester are added and heating is carried out at from 100 to110° C. under reflux. That temperature is maintained for 3 hours and thewater that forms is removed using a separator. Most of the toluene isthen distilled off and the residue is dissolved in 80 ml of petroleumether (boiling range 80-110° C.) in the hot state and clarified byfiltration. On slow cooling, the compound of formula

[0117] crystallises out and, at 25° C., is filtered off. After drying,7.1 g of yellow crystals having a melting point of 75-77° C. areobtained.

[0118] ε=62081 in ethanol l/(mol/cm) at λ_(max)=434 nm,

[0119] elemental analysis for C₂₄H₃₂N₂O₂[%]: C H N O calculated 75.758.48 7.37 8.41 found 75.7 8.5 7.4 8.6

Example 3

[0120] 17.3 g of 1,3,3-trimethyl-2-methylene-indoline (=Fischer base)are dissolved in 30 ml of methylene chloride and, over the course ofhalf an hour, 14 g of benzoyl chloride are added dropwise at 20-32° C.The reaction mass is heated to 45° C. and that temperature is maintainedfor half an hour; the reaction mixture is cooled to 25° C. and theprecipitated hydrochloride of the starting material is filtered off. Thered filtrate is concentrated to dryness and recrystallised from amixture of 30 ml of acetone/3 ml of water. 8.7 g of the compound offormula

[0121] are thereby obtained in the form of pale yellow crystals having amelting point of 133-134° C.

[0122] ε=29427 in dioxane l/(mol/cm) at λ_(max)=377 nm.

APPLICATION EXAMPLES Example 4 Preparation of an O/W Lotion

[0123] INCI name % polyglyceryl-3 methylglucose distearate 3.0 decyloleate 7.2 isopropyl palmitate 7.0 caprylic/capric triglyceride 8.4compound of formula (103) 4.0 octyl methoxycinnamate 5.0 glycerol 3.0phenoxyethanol & (methyl, ethyl, propyl, butyl) parabens 0.5 deionisedwater 60.9 carbomer 0.2 isopropyl palmitate 0.8 NaOH (10%) as required

[0124] The oil phase and the aqueous phase are separately heated to75-80° C. and cautiously brought together. That is followed by intensivehomogenisation and cooling to room temperature with gentle stirring.

[0125] Using an Optometrics SPF-290 Analyzer (2 μl/cm² on Transporefilm) an in vitro SPF of 15 is determined. The Australian standard forUVA protection (Australian/New Zealand Standard, 15/NZS 2604: 1993) ismet.

Example 5 Preparation of an O/W Emulsion

[0126] INCI name % A polyglyceryl-3 methylglucose distearate 2.5 decyloleate 7.7 isopropyl palmitate 7.0 vitamin E acetate 1.5 caprylic/caprictriglyceride 9.5 bis-octylphenol methoxyphenyl triazine 3.0 compound offormula (101) 3.5 B glycerol 3.0 phenoxyethanol & (methyl, ethyl,propyl, butyl) 0.5 parabens deionised water 64.3 C carbomer 0.2isopropyl palmitate 0.8 E NaOH (10%) as required

[0127] Phase C is combined with phase B and then phases A and B areseparately heated to 75-80° C., cautiously brought together andhomogenised. After cooling with slow stirring, the pH is adjusted to 7.0using E.

[0128] Using an Optometrics SPF-290 Analyzer (2 μl/cm² on Transporefilm) an in vitro SPF of 18 is determined. The Australian standard forUVA protection (Australian/New Zealand Standard, 15/NZS 2604: 1993) ismet.

Example 6 Preparation of a W/O Emulsion

[0129] INCI % w/w PEG-30 dipolyhydroxy-stearate 3.50 PEG-22/dodecylglycol copolymer 1.50 microcrystalline wax 1.00 hydrogenated castor oil1.00 magnesium stearate 1.00 octyl stearate 15.00 coco glycerides 2.00mineral oil 3.00 phenoxyethanols and (methyl, ethyl, propyl, butyl)parabens 1.00 octyl methoxycinnamate 5.00 dimethicone 0.10 deionisedwater 49.90 allantoin 0.10 magnesium sulfate 1.00 compound of formula(102) 5.00 propylene glycols 4.00 methylene bis-benzotriazolyltetramethylbutylphenol (pH 5.5) 6.00

[0130] The oil phase and the water phase are separately heated to 75-80°C. and cautiously brought together. That is followed by intensivehomogenisation and cooling to room temperature with gentle stirring.Methylene bis-benzotriazolyl tetramethylbutylphenol is mixed into theemulsion obtained, with stirring.

[0131] Using an Optometrics SPF-290 Analyzer (2 μl/cm² on Transporefilm) an in vitro SPF of 24 is determined.

Example 7 Preparation of a W/O Emulsion

[0132] formulation formulation INCI name (A) % (B) % methoxyPEG-22/dodecyl glycol copolymer 3.00 3.00 PEG-22/dodecyl glycolcopolymer 3.00 3.00 hydroxyoctacosanyl hydroxystearate 3.00 3.00 octylstearate 15.00 15.00 coco glycerides 2.00 2.00 mineral oil 3.00 3.00phenoxyethanols and (methyl, ethyl, 1.00 1.00 propyl, butyl) parabensoctyl methoxycinnamate 4.00 5.00 dimethicone 0.20 0.10 deionised water47.70 43.80 allantoin 0.10 0.10 compound of formula (102) 5.00 4.00magnesium sulfate 1.00 1.00 propylene glycols 4.00 4.00 methylenebis-benzotriazolyl 8.00 12.00 tetramethylbutylphenol (pH 5.5) (50%suspension)

[0133] The oil phase and the aqueous phase are separately heated to75-80° C. and cautiously brought together. That is followed by intensivehomogenisation and cooling to room temperature with gentle stirring.Methylene bis-benzotriazolyl tetramethylbutylphenol is added to theemulsion obtained, with stirring.

[0134] Using an Optometrics SPF-290 Analyzer (2 μl/cm² on Transporefilm) in vitro SPF values of 20 (A) and 28 (B) are determined. TheAustralian standard for UVA protection (Australian/New Zealand Standard,15/NZS 2604: 1993) is met.

1. Use of an indoline derivative of formula

wherein R₁ is hydrogen; C₁-C₅alkyl; C₁-C₁₈alkoxy; or halogen; R₂ isC₁-C₈alkyl; C₅-C₇cycloalkyl; C₆-C₁₀aryl; R₃ is C₁-C₁₈alkyl; or a radicalof formula (1a)

R₄ is hydrogen; or a radical of formula (1b)

R₅ is a radical of formula (1c)

C₁-C₁₈alkoxy; or a radical of formula

R₆ and R₇ are each independently of the other hydrogen; or C₁-C₅alkyl;R₈ is hydrogen; C₁-C₅alkyl; C₅-C₇cycloalkyl; phenyl; phenyl-C₁-C₃alkyl;R₉ is C₁-C₁₈alkyl; X is halogen; a radical of formula (1e)

or

and n is 0;or 1, as a light-protective agent.
 2. Use according to claim1, wherein, in formula (1), R₅ is a radical of formula (1g)

and R₈ is hydrogen; C₁-C₅alkyl; or phenyl.
 3. Use according to claim 2,wherein R₈ is hydrogen or methyl.
 4. Use according to claim 2, whereinR₅ is C₁-C₁₈alkoxy.
 5. Use according to claim 4, wherein R₅ is a radicalof formula (1h)


6. Use according to claim 1, wherein R₅ is a radical of formula (1i)

and R₈ is hydrogen; or methyl.
 7. Use according to any one of claims 1to 6, wherein R₃ is C₃-C₁₈isoalkyl.
 8. Use of a compound of formula (1)in protecting human and animal hair and the skin against the damagingaction of UV radiation.
 9. A cosmetic composition comprising at leastone or more compounds of formula (1) according to claim 1 together withcosmetically tolerable carriers or adjuvants.
 10. A compositionaccording to claim 9, which comprises further UV-protective substances.11. A composition according to either claim 9 or claim 10, whichcomprises triazines, oxanilides, triazoles, vinyl-group-containingamides or cinnamic acid amides as further UV-protective substances. 12.A compound of formula

wherein R₁ is hydrogen; C₁-C₅alkyl; C₁-C₅alkoxy; or halogen; R₂ isC₁-C₅alkyl; C₅-C₇cycloalkyl; C₆-C₁₀aryl; R₃ is C₁-C₅alkyl or a radicalof formula (1a)

R₄ is hydrogen; or a radical of formula (1b)

R₅ is C₅-C₁₈alkoxy; a radical of formula (1b); or a radical of formula

R₉ is C₁-C₁₈alkyl; or R₄ and R₅ denote a radical of formula (1b).